7/14/2019 CHAPTER 7-Lecture Notes thermo

MATERIALS
THERMODYNAMICS II

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Chapter 7

PHASE EQUILIBRIUM IN
A ONE – COMPONENT
SYSTEM

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Thermodynamic Properties of a
System

1. Extensive Properties, which are additive.

• Mass, volume, energy, etc.
2. Intensive Properties, to which a value may be
assigned at each point in the system.
• Temperature, pressure, chemical potential,
etc.

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Intensive Properties

•
Temperature: Measure of the tendency for heat
to leave the system.
•  Pressure: Measure of the potential of a system
to undergo massive movement by expansion or 
contraction.
• Chemical potential : Measure of the rate of 
energy change of a system with the change in
the amount of  ith component where all other 
variables being held constant.

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Complete thermodynamic equilibrium is said to

 prevail when the system under consideration is
in mechanical (pressure is same at all points),
thermal (no temperature gradient) and chemical 
equilibrium (Gibbs chemical potential of each

component must be equal).

In a closed system of fixed composition, e.g., a

one-component system, equilibrium, at the
temperature, T, and the pressure, P, occurs when
the system exists in that state which has the
minimum value of G.
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The Gibbs free energy of the system, G  , is independent of the ’ 

 proportions of the ice phase and the water phase present.

at const. T&P

The chemical potential of species in a particular state equals the

molar Gibbs free energy of the species in that particular state.
(P =1 atm, T = 273 K)
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If P=1 atm and T > 273 K,  () <  () 
T < 273 K,
  () >  ()  


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7/14/2019 CHAPTER 7-Lecture Notes thermo

∆ 

Hess’s Law 

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ΔG=ΔH-TΔS 

• At all T, H(l) > H(s)

S(l) > S(s) 
So solid will be stable at
  s
  e
   l
  u
  o all T.
   J • However,
ΔG=ΔH-TΔS 
• Therefore, at T < Tm,
ΔH(s→l) > TΔS(s→l) 
whereas at T > Tm,
ΔH(s→l) < TΔS(s→l) 
273 T (K)

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Variation of G with P at Constant T

Const T (273 K)


    =

G  
For water: V(s) > V(l) 

1 atm
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G as a Function of T & P
For equilibrium to be maintained:
G(l) = G(s) dG(l) = dG(s) 
V(l) dP - S(l) dT = V(s) dP - S(s) dT 


  = (→)
 =    Clapeyron eqn.

ΔV < 0 for H2O and

ΔH>0 for all materials:
 <0


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P 0.0075 °C ,
0.006 atm
0 °C, 1 atm

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7/14/2019 CHAPTER 7-Lecture Notes thermo

Equilibrium between vapor phase and a

condensed phase

 =    Vvapor  >> Vcond.phase  ΔV ≈ Vvapor 

   

Assuming vapor behave as ideal gas:

 =    = 
  

  
dlnP 

=  eqn.
  
Clasius-Clapeyron
 

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7/14/2019 CHAPTER 7-Lecture Notes thermo

• If ΔH is independent from T:

c p(vapor) = c p(cond.phase)

 = 
 +.  

• If ΔC p≠ 0, but independent of T: ΔC p = const.


 
 =  298 + 
 +  =  +    298
 =    
  
 = 298    1 +   +.  

 =  +  +  
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7/14/2019 CHAPTER 7-Lecture Notes thermo

For H2O:
30+10.7 10-3T+0.33 105T-2 J/K (298-2500 K)
, 
 ()
 ==41,090 J
() 
75.44 J/K (273-373 K)
.

, = , +  (→) 

.   
57,383-45.44T+5.35 10-3 2
T-  
= x 

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7/14/2019 CHAPTER 7-Lecture Notes thermo

dlnP 

=    and R-8.314 J/K mole

 =  6,901. 64  5.465  + 6.435 × 10− + 1,984.509

+. 
Since the normal boiling point of the liquid is defined as the
temperature at which the saturated vapor pressure exerted by the
liquid is 1 atm, P=1 atm at 373K.
const=50.62

Thus the variation of the saturated vapor pressure of water with T 

in the range 273-373K:
2997 862
 =   5.465  +0.279× 10  +  +21.98 
−
 
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A
B

m b
1

   ) liquid
  m solid
   t
  a
   (
  e
  r
  u
  s
C’ 
  s
  e 0.006
  r
   P O
B’ 
vapor 
A’ 

0 0.0075 100

Temperature ( °C)
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Gibbs Phase Rule

•

Single phase areas have two degrees of freedom since T and P

can be altered independently without disturbing the
equilibrium.
• While the equilibrium through , , and lines,
which indicates two phase equilibrium, can be maintained by
AO BO CO
changing only one variable, either T or P. Therefore, they have
only one degree of freedom.
• On the other hand, tripoint junction has zero degrees of 
freedom.
•

These criteria result in the Gibbs phase rule:

F=C-P+2
• Taking F=0 gives the maximum number of phases that can be
observed for a given number of species.

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7/14/2019 CHAPTER 7-Lecture Notes thermo

l
Since 
G = S :
P1 
s  ,o
   P a  b
o all of the slopes are negative
v
and since S(v) > S(l) > S(s) :
T
slopes are increasing from solid
v to vapor.
l

s
   G SKETCH G-P DIAGRAM
FOR GIVEN T WITH THE
BLUE COLOR LINE!!!

T
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7/14/2019 CHAPTER 7-Lecture Notes thermo

Example Problem 1

The vapor pressure of solid NaF varies with temperature as

 
lnP atm = 34,T450  2.01 lnT + 33.74
and the vapor pressure of liquid NaF varies with temperature as
lnP atm = 31, 090  2.52 lnT + 34.66 
•
T
Calculate the the normal boiling temperature of NaF.
The normal boiling temperature,Tb , is defined as that temperature
at which the saturated vapor pressure of the liquid is 1 atm.
ln 1 = 0 = 31,T090  2.52 lnT + 34.66 
 

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• Calculate the temperature and pressure at the triple point.

The saturated vapor pressures for the solid and liquid phases
intersect at the triple point, .
T
34,450  2.01 lnT + 33.74 = 31,090  2.52 lnT +34.66 
T T
 
T = 1239K

The pressure at the triple point can be calculated either from the
vapor pressure of solid or vapor pressure of liquid equation.

34, 450
P = exp 1239  2.01 ln1239 + 33.74  
−atm
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• Calculate the molar heat of evaporation of NaF at its normal

 boiling temperature.

For vapor in equilibrium with liquid:

31, 090
lnP atm = T  2.52 lnT + 34.66 
From Clasius-Clapeyron equation:

dlnP = ∆H = 31,090  2.52 

dT RT T T
Since R=8,314 J/molK and is 2006 K:
Tb
∆H = 31,090×8.314  2.52×8.314×2006  
 
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• Calculate the molar heat of melting of NaF at the triple point.

For vapor in equilibrium with solid:

lnP atm = 34,T450  2.01 lnT + 33.74  

From the previous case,we know that:

∆H(→v)=  31,090×8.314  2.52×8.314×T  
And it is obvious that:
∆H(s→v)=  34,450×8.314  2.01×8.314×T  
Since ∆H(s→) + ∆H(→v) = ∆H(s→v) :
 
∆H = 27,900 + 4.24T
(s→)
Since T = 1239 K:
 

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• Calculate the difference between the constant-pressure molar 

heat capacities of liquid and solid NaF.
As we know
∆→ = ∆(→) 

Since :
∆H = 27,900+ 4.24T
(s→)
∆(→)= ∆()  ∆  = 4.24 /K 

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Example Problem 2

• The vapor pressures of zinc have been written as

lnP atm = 15,T780  0.755 lnT + 19.25 

lnP atm = 15, 250  1.255 lnT + 21.79 
•

T
Which of the two equations is for solid zinc?

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Example Problem 3

• Below the triple point (-56.2°C) the vapor pressure of solid

CO2 is given as:
3116
lnP atm = T +16.01 
• The molar latent heat of melting of CO2 is 8330 J and normal
melting temperature of CO2 is -57 °C.
• Calculate the vapor pressure exerted by liquid CO2 at 25 °C
and explain why solid CO2 is referred to as “dry ice.” 

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Homework 

• Carbon has three allotropes: graphite, diamond, and a metallic

form called solid III. Graphite is the stable form of 298 K and
1 atm pressure, and increasing the pressure on graphite at
temperatures less than 1440 K causes the transformation of 
graphite to diamond and then the transformation of diamond to
solid III.
• Calculate the pressure which, when applied to graphite at 298
K, causes the transformation of graphite to diamond.
• Given:
H (Grhi)  H  Dio = 1900J  
 
S (Dio) = 5.2.7347J/K
 (Grhi) J/K 
ρ (Grhi) = 2.22 g/cm 
ρ (Dio) = 3.515 g/cm  
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